Disazo-dyestuffs



United States Patent 2 4: 6: B-tetrabromo-1E5 diarninoanthraquinone, 2798 064 1.:Sedichloro-ZE6-diarninoanthraquinone, 1:5:-dibromo-2':diaminoanthraquinone, 1 DISAZO DYESTUFFS 3 :7-dibromo-2: o-diaminoanthraquinone,

1:3:5: -t -2: -d' Willy Mueller, Riehem switzerland;assignor to CibaLim- 3 li tgigi g 3 55 322322: umone ited, Basel, Switzerland; 2:Swissfirm As azo components there come into considerationcompoundswhich are also free from groups imparting solubility and whichare capable of coupling in a; position No Drawing. Application September8, 1953, "Serial No. 379,685

Claims priority, ,applieation switzeriand 10 vicin'al to a hydroxylgroup. The hydroxyl group may September 12, 1952 I be a hydroxyl groupbound to an aryl carbon atom or an 4 Claims. 1 (Ch 260;;176) .JEIlOllZCdketo group.

Among the azo components of the. kind first mentioned 'above,..forexample, there may beused hydroxynaph- This. inventionprovidesanew,waterainsoluble.disazothalelles ap of Coupling in 3Position Vieillal t0 the dyestufis which,like.thedyestutf of the formula*hy y group, such as yy ap NH-CO :CN=-N H3cc on a aw.

' N=NC GO-HN correspond to the general'formula H 1 -.1hydr,oxy 5:8dichloronaphthalene,. 2 -.hydroxynaph- Jtha ene orZ-hydroxy-6-bromonaphthalene. 'Ihere are (2) R2 'N=N R1 N=N R2alsousef-ul azo components which. contain-a carboxylic in which R1represents an anthraquinoneradicalzfreevfrom acid-.aryltamide; group ina position .vicinal .to the hygroups imparting solubility and inwhichthe :two :carbon .droxylgroup imparting coupling properties andbound atoms to which the azolinkages are. bound. are.s eparated*.35 toanaryl carbon atom. As examplesithere may be menfrom one another byatleast three carbonatomsofathe 'tioned 2-hydroxynaphthalene-3-carboxylicacid ,naphanthraqui-none.nucleus, and R2 represents the. radicalhof.sthyl-(1) amid,.-phenylamide or .-2-methoxyphenylamide, anazo-component freefrom. groups impartingsolubilityi2-hydroxycarbazole-3-carboxylic .acid anilide or -4- and bound to theazo-linkage in a position yicinalto ahychloranilide, 2hydroxydiphenylene .oxide 3-carboxylic droxyl group. 40 acid..anilide.or -2:5'-dimethoxyanilide.

The inventionalso includes a process forma'king disazo- .As azocomponents in which coupling takes .place i a dyestuffs 0f the abovelgenefal formularwhel'eihaletmlo 1 positionvicinalto an enolizableketorgroup,,there.may, be compound of a diaminoallthfaquihoneswhieh'isffee from mentioned for example, barbituric acid,acylacetylamino groups imparting Solubility and in whieh'the five-carboncompounds and pyrazolones. Among the acylacetylamino atoms to which thediazotized amino groups areboundr nd th may be usedacylacety-laminoearyl,c are separated from one another by at least threecarbon d f l benzoylacetyl i 1 atoms Of thfi anthraquinone nucleus, iscoupled With an 1 pgunds, and especially acetoacetylamino .ary1 cum.Component free from groups imparting Solubility all-1d pounds ofthebenzene series. ..The. aryl radical. bound capable of Coupling in aP05ition Vicinal 10 y y to.tthe .acyl'acetylamino group may-contain,.in. addition groupto thlS.wg1O1lP, other. substituentsincapable. of imparting A Will be Understood from the foregoingdefinition, .solubility such, for example; asialkyl or alkoxy groups theamino groups must not be bound to the same 641mm of low-.molecularweights .or. .halogeniatomst such. as bered ring of the anthraquinonenucleus. In additiorrto ,chlorinmkand l agetylamino groups or sulfonic aid the amino groups, the anthl'aquinene nucleus y C011" amide groups.There also come into consideration azo ra n further Substituents,especially halogen atoms, Such components of which the acyl acetylaminogroup is bound as bromine of chlorine AS examples of Suitable m n to acarbon atom in a heterocyclic ring. As examples of enthraquinones therey be--mentined the fhllewing suitable azo components there may bementioned l-ben- Compounds! zoylacetylaminobenzene, 1benzoylacetylamino-2-methoxy-S-methylbenzene and also acetoacetylaminocompounds derived from the following amines of the benzene series:Aminobenzene, l-amino-Z-chlorobenzene, 1

1 S-diaminoanthratruinone, 1 6-diaminoanthraquinone, 1':7-diaminoanthraquinone,

2:6-diaminoanthraquinone, amino 4 methylbenzene,1-amino-2-methoxybenzene, 1- 2:7-diaminoai1thraquinone, amino 2:5dichlorobenzene, 1 ammo-2:4-d1methyl-5-4:8'-di'ch1oro-1:S-diaminoanthraquinone, chlorobenzene, 1am1no-2-chlorol-acetylammo-S-metb2:4:6z8-tetrachloro-1:S-diaminoanthraquinone, oxybenzene, 1amino-2-chloro-S-tnfluoromethylbenzene,2:6-dibromo-1:S-diaminoanthraquinone, 1 amino2z5-dimethoxy-4-chlorobenzene, l-arnnobeny -S-pyrazolone.

The diaminoanthraquinones are tetrazotized in known manner,advantageously in concentrated sulfuric acid by means of an alkalinitrite. It is usually of advantage to precipitate and isolate thetetrazo-compound.

The tetrazo-compound so obtained are advantageously coupled with the azocomponents of the aforesaid kind in a weakly acid, for example, aceticacid medium, and it is generally of advantage toadd a wetting ordispersing agent to the coupling mixture. For this purpose wetting anddispersing agents of ionogenic or non-ionogenic character may be used.As ionogenic dispersing agents there may be used, for example Turkey redoil, and as nonionogenic dispersing agents there may be used polyglycolethers of fatty alcohols of high molecular weight.

The new disazo-dyestufis corresponding to the above Formula 2 arevaluable pigments and are usually distinguished by their especially goodfastness to migration and also by their heat resistance and fastness tosolvents.

These properties are valuable, for example, for so-called pigmentprinting, that is to say, printing processes in which a pigment is fixedon a substratum, especially a textile fiber or another sheet-likestructure such as paper (for example, wallpaper) or fabrics of glassfibers, by means of a suitable adhesive such as casein, a hardenableartificial plastic, especially a urea-fomaldehyde ormelamine-formaldehyde condensation product, solutions or emulsions ofpolyvinyl chloride or polyvinyl acetate or other emulsions (for example,oil-in-water or water-inoil emulsions). The new pigments can also beused with good results for other purposes, for example, in a finelydispersed form for dyeing artificial silk from viscose or celluloseethers or esters or of superpolyamides or super:

polyurethanes in the spinning mass, and also for the manu facture ofcolored lacquers or lacquer formers, solutions or products ofacetyl-cellulose, nitrocellulose, natural resins or artificial resinssuch as polymerisation or condensation resins for example, aminoplasts,phenoplasts,

'polyvinyl chloride, polystyrene, polyethylene, polyacryl,

rubber, casein, silicone and silicone resins. Furthermore, they are alsoof advantage for the manufacture of 100 parts of water.

4 tions, such as spinning, pressing, hardening, casting, sticking or thelike, may be carried out directly in the presence of the pigments,without inhibiting any chemical reactions which the substrata are toundergo such as further polymerisation, condensation etc.

The following examples, illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relationshipof parts by weight to parts by volume being the same. as that of thekilogram to the liter:

Example 1 400 parts of sulfuric acid of 98 percent strength are cooledto 0 C., and 28 parts of sodium nitrite of 100 percent are introducedWhile stirring at 5l0 C. The whole is then heated to -60 C. until aclear solution is obtained, the solution is then cooled to 30 C., and47.6 parts of 1:5-diaminoanthraquinone are introduced at 3040 C., whilestirring. A thick yellow suspension is formed. When the addition iscomplete the whole is slowly heated to 5060 C. until a clear solution isobtained, the solution is then cooled to 30 C., and the solution ismaintained at that temperature for a further 30 minutes. The Whole isthen allowed to cool to 30 C., and the solution is poured on to 600parts of ice and In this manner the tetrazo-compound crystallizes out inyellowish white crystals. The mixture is stirred for a further 30minutes at 0-5 C., and then filtered and the filter residue is pressedwell. The tetrazocompound remains unchanged in the moist state forseveral weeks when stored in the cold with the exclusion of light. p

42.3 parts o f 1-acetoacetylamino-2-chlorobenzene are dissolved by meansof 30 parts of sodium hydroxide solution of 3Qpercent strength in 300parts of water at 30 C.

A dispersing agent such, for example, as Turkey red oil,

is added, and the solution is made up to 800 parts by volume by theaddition of ice and water and is thereby given the temperature of 5 C.The whole is then acidified with dilute acetic acid-until the reactionis acid to litmus, parts of crystalline sodium acetate are added, and asolution of the tetrazo-compound from 23.8 parts of1:5-diaminoanthraquinone in 1000 parts of water is added while stirringin the course of about 30 minutes. The whole is stirred for 2 hours at5-8 C., and then heated in the course of one hour to 35-40" C. andstirred at that temperature for a further 4 hours. The waterinsolubleyellow dyestufl so formed is filtered off, washed free from salts with alarge quantity of water, and dried in vacuo at 50 C. There is obtained ayellow powder which dissolves in concentrated sulfuric acid with aredrated by rolling into polyvinyl chloride, strong pure greenish yellowcolorations having very good properties. This dyestutf corresponds tothe formula in the following table" are given" "a' "few .fu'rtheridisazo""dye'stufis obtainable. in the manner described in this 'example from 1"mol of I tetrazoti'zed. 1: S-diaminO anthra- .fquinone and. 2mols oftheazo components set outin i'colume. I,which"dyestufist'yieldfwhen"incorporated by rollingintopolyvinylchloride, the tinsfligivenin column agweed;

Example 3 42.3 part i of: 1'-acetoacetylamino 2 chlorobenzenearedissolved with 30sparts of 'sodiumhydroxide solution of 30 percent-.strength in: 3'00"parts of water. After the addition ofa dispersingagent, for example,:Turkey red oil, :thelsolution isI-made up to 800parts-by -volume and given atemper'ature'of5 Cfby the addition of iceand t I. Azocompouent ,wate r. Then whole is then mixed with: diluteacetio acid l-Acetoacetylamino-2-rnethoxybenzenerobenzene.

l-Acetoacetylamino-2-chloro-4-acetyll-Acetoacetylamino-2-chloro-5-trifluoromethylbenzene.

zole

. l-Aeetoacetylamino-2:5-dimethoxy-4- chlorobenzene.

l-Acetoacetylaminobenzene-ti-sulionic acidamidel-Acet'oacetylitmino-Z-methoxy-5-methylbenzene.l-PhenyI-B-methyl-E-pyrazolone ne.1-Benzoylacetylamino-Z-methoxy-fi-methylbenzene.

l-Acetoacetylamino-2;5 dichlorobenzenel-Acetoacetylamino-2:4-di.methyl-5-chlo- Iminutes -while stirring well,into a suspensionof l-acetoacetylamino-Z-chlorobenzene, and the whole isstirred for 2 hours at 5-8 C. The whole is then slowly heated 'to 40'-50C; arid stirred for a further 4 hoursat that greenish yellow.

yellowishorange.

oran 6'.

i t-erri giei'ature. The dyestiifi formed is-then filtered 0115 andwashed free*"-from=-salts-with water. 'After drying thedyestufiifl'vacuo. it is obtained in the form-of a yellow "reddishorange. "'p wderf'which dissolves in concentrated sulfuric acid With'ayellow-coloration. When'incorporated by rolling reddish yellow. intopolyvinyl chloride the-dyestufl yields strong greenish yellow'tintsof'very good fastness to migration and light.

Following i the formula of a representative-dyestutf of theforegoingtable:

' 58.6 parts parts or Water.

Inthe following table are given a few furtherdisazo dyestuffsobtainable'inthe manner described in this exam'ple'from 1 mol oftetrazotized 2:6-diaminoantl1raquinone and 2-mols of the azo componentsgiven in column I.

of 1-(2'-hydroXy-3'-naphthoylamino)-2- methox'ybenzene are dissolvedWith the' aid of parts "of'sodiu'm hydroxide solution of 30 percentstrength and 100 parts of alcohol in 800 parts of water. A-dispersing'agent such as Turkey red oil is added, the mixture is made up with iceand Water to 1200 parts:byvolume whereby it i given the temperature of 0'C., and then acidified with dilute acetic acid" until 'the rnixtureturns 7 litmus red. After the addition of 60 parts'of 'crystal- 4 linesodium acetatefthe whole is run in the course of about 30 minutes into asolution of the tetrazo compound from 23.8 parts of1:5-diaminoanthraquinone in 1000 The whole is stirred for 2 hours at 510C... then slowly heated-to 40-45 C. and stirred for a further 4 hour atthat temperature. "The waterinsoluble dyestufi formed is thenfiltered'off. and washed free from salts with water. "After' drying it in vacuoat I. Azo component II. Tint on polyvinyl chloridel-Acetoacetylamiuobenzene greenish yellow. 1 Acetoacetylamino 2:5'dichloro- Do. benzene. 1 Acet'oaeetylamino 4'- methyl ben Do.

zene. 1 Acetoacetylamino i 2 methoxyben- -pure yellow.

zene. 5 1 Acetoacetylamino 2:5 -'dimethoxy Do.

l-chlorobenzene. V 1 (2 chlorophenyl) 3 methyl 5 yellowish orange.pyrazolone. 7 2 -'Hydroxy 3 naphthoylamiuo pure red.

' benzene. 8 1 (2 Hydroxy- 3 naphthoylamino)- bluish red.

2-methoxybenzene.

Example 4 5060 C. there is obtained a dark red powder, which dissolvesin concentrated sulfuric acid with a blue-red 5 coloration and givesstrong bluish red colorations-of good fastness to migration andlight'when incorporated in poly-' vinyl chloride.

By using in this example,.in'stead of 1-(2'-hydroxy -'3'-naphthoylamino)-2-methoxybenzene, the corresponding quantity of 1'-2-hydroxy- "-riaphthoylamino)-benzene, there. .is obtainedfa'dye'stiiffWhich dissolves in concen- "'trated sulfuric acid with a red colorationand gives powerful-pu're red tints of good fastness to light whenincorporatediin polyvinyl chloride.

67.3 parts of 2-hydroxycarbazole-3-carboxylic acid- (4'-chlor)-anilideare dissolved with the aid of 30 parts of sodium hydroxide solution of30 percent strength and v. parts of alcohol in 800 parts of water. Adispersing agent such as Turkey red oil is added, the mixture is made upto 1200 parts by volume and given a temperature of 5 C. by the additionof ice and water, and the whole is acidified with dilute acetic aciduntil its turns litmus red. After the addition of 60 parts ofcrystalline sodium acetate, there is run in in the course of about 1 /2hours 5 a solution of the tetrazo compound from 23.8 parts of 71:5-diaminoanthraquinone in 1000 parts of water. The whole is stirredfor 2 hours at 8l2 C., then slowly :heated to, 50? C., and the whole isstirred at that temperaturefor 6 hours The dyestuff formed is thenfiltered off and-washed with hot water untilthe filtrate is practicallyfree ,from salts; After-drying the product in vacuo at :,506 0 'C.,there is obtained. a brown powder, which ,dissolves inconcentrated,sulfuricflacid with a blue. colora- ;.tion and yieldsstrongbrown tints when incorporated by rolling into polyvinyl chloride: 1

By using in this example, instead of 2-hydroxycarbaiole- 3-carboxylic'acid-(4'-chlor)-anilide, the corresponding quantity ofZ-hydr'oxydiphenylene: oxide-3-carboxylicacid-('2':5'-dimethoXy)-anilide, there is obtained a blackbrown powderwhich dissolves in concentrated sulfuric acid with a violet colorationand yields strong dark brown tints when incorporated by rolling intopolyvinyl chloride.

V A Example 5 V 1426: parts of I 5:8-dichloro 1 hydroxynaphthalene are Idissolvedin SOOparts of water with the aid of 30 parts ofsodiumhydroxide' solution of 30 percent strength.

l' After the addition ofa dispersing agent such as Turkey red oil, thesolution is made up to 800 parts by volume ..and. given a temperature ofC. with ice and water. The whole is then mixed with dilute acetic aciduntil the reaction is acid to litmus, and 60 parts of crystalline sodiumacetate are added. At the same time 23.8 parts ofl:S-diaminoanthraquinone are tetrazotized as described the firstparagraph of Example 1, and the separated tetrazo-compound is dissolvedin 1000 parts of water. The clear solution of the tetrazo-compound isrun, while stirring, at 10-15 C. into the coupling suspension, and thewhole is stirred for 2 hours at l0l5 C. The whole is then slowly heatedto 30-40 C., and stirring is continued for a further 4 hours at thattemperature. The precipitated dyestuff is then filtered off and washedfree from salts with hot water. After drying the product in vacuo at6070 C., there is obtained a dark red soft powder, which dissolves inconcentrated sulfuric acid with a blue green coloration and yieldsstrong red-tints when incorporated by rolling into polyvinyl chloride.

By using in this example, instead of 1:5-diaminoanthraquinone, the samequantity of 2:6-diaminoanthraquinone as tetrazo component, there isobtained a bright red powder which dissolves in concentrated sulfuricacid with a blue green coloration and yields powerful red tintswhenincorporated by rolling into polyvinyl chloride.

Example 6 160 parts of concentrated sulfuric acid are cooled to 0 C.,and then 14 parts of sodium nitrite of 100 percent strength areintroduced at 010 C. The whole is then slowly heated to 50-60 C. until aclear solution is obtained, the solution is then cooled to 30 C., and39.6 parts of 2:6-diamino-3:7-dibromanthraquinone are added at 3040 C.,while stirring. The whole is then stirred for one hour at 50-55 C.,cooled to 15 C., and the solution is poured on to 300 parts of ice. Inthis manner the tetrazo-compound crystallizes out in the form of yellowcrystals. The whole is stirred for one hour at 0-5 C., and the crystalsare filtered off and washed with a small amount of ice water.

42.3. parts of 1-acetoacetylamino-Z-chlorobenzene are strength. Adispersing agent such as Turkey red oil is added, and the solution ismade up to 800 parts by volume and given a temperature of 10 C(by theaddition of ice and water. The solution'is then acidified with diluteacetic acid until the reaction is acid to litmus, 60 parts ofcrystalline sodium acetate are added, and the tetrazo-compounddissolved'in 1000 parts of water is run in, while stirring, in thecourse of about one hour. The whole is then stirred for 2 hours at 10-15C., heated to 4050 C., and stirred for 4 hours at that temperature. Thewater insoluble yellow dyestuff so formed is then filtered off, washedfree from salts with hot water, and dried in vacuo at -60 ,C. Thereisobtained a yellow powder which dissolves in concentrated sulfuric acidwith a red yellow coloration and yields strong yellow tints having goodproperties of fastness when incorporated by rolling into polyvinylchloride.

Dyestuffs having similar properties are obtained by using this example,instead of 2:6-diamino-3z7-dibromanthraquinone, the correspondingquantity of 2:6-diamino-1 :3 5 7-tetrabromanthraquinone or 2:6-diamin 1:S-dichloranthraquinone.

Example 7 in which R1 represents an anthraquinone radical free fromgroups imparting water-solubility containing as substituentsfin additionto the two azo linkages, at most halogen atoms selected from the groupconsisting of chlorine and bromine atoms, and in which the two carbonatoms to which the azo linkages are bound are separated from one anotherby at least three carbon atoms of the anthraquinone nucleus, and R2represents an acetoacetylaminobenzene radical free from groups impartingwater-solubility and bound to the azo linkage in u-position vicinal to ahydroxyl group.

2. A disazo dyestufi of the formula in which R2 represents a benzeneradical free from groups imparting water-solubility.

3. The .disazo dyestufi of the formula 9 10 4. The disazo dyestuff ofthe formula CN=N 0- 0 I H C-GHa OF] N=N-O References Cited in the fileof this patent UNITED STATES PATENTS 1,121,026 Laska et a1 Dec. 15, 19141,505,568 Laska et a1 Aug. 19, 1924 2,115,412 Dahlen et a1. Apr. 26,1938 2,457,823 Kendall Jan. 4, 1949 OTHER REFERENCES Kacer et a1.: Ber.Deut. Chem., vol. 37, 1905, pages 4185-4187.

v for "tetrazo-compound" read UNITED STATES PATENT oEFlcE CERTIFICATE OFCORRECTION Patent No. 2,798,064 J ly 2, 1957 Willy Mueller It is herebycertified that error appears in the printed specification of the abovenumbered patent requiring correction and that the said Let cers Patentshould read as corrected below.

"amid," read amide, column 3, line 22, tetrazo-compounds column 4, line6, the comma; column 5 line 6, for "tins line 22, after "using" insertin ---0 Column 2, line 37, for

after exemples" strike out read tints column 8,

Signed and sealed this 24th day of September 1957.

(SEAL) Attest:

KARL LINE ROBERT c. WATSON Attesting Officer Comisaioner of Patents

1. A DISAZO DYESTUFF OF THE FORMULA